High wet fast disperse dyes and mixtures thereof

ABSTRACT

Dyes of formula (1) 
     
       
         
         
             
             
         
       
     
     their production and their use.

This invention relates to disperse azo dyes and their mixtures.

Disperse dyes with improved fastness properties, especially washfastness are of growing interest.

Disperse dyes having 2,4,6-Di-nitro-halogen diazo-component (a) asstructural element are well known and are the basis of most red andespecially violet and blue disperse dyes and mixtures using those dyes.

Dyes according to (a) and their preparation are known and described invarious patents e.g. GB 2030169, DE 4335261, DE 3112427, DE 2818653, WO2005/056690 or EP 0 240 902 but are having deficits in light- andwet-fastness properties. Dyes of formula (a) where the halogen is fluoroare rarely exemplified.

The substitution pattern 2,4,5-Dinitro-halogen according to (b) is alsoknown e.g. from WO 2005/056690 or WO 2005/040283. In combination withspecial coupling components they may result in dyes with improvedfastness properties.

Still though there remains a need for disperse dyes, which providedyeings of improved fastness properties of dyed polyester or its blendswith other fibres such as cellulose, nylon, elastane and wool.

Surprisingly it was found that 2,4,5-Dinitro-fluoro-aniline as a diazocomponent delivers disperse azo dyes and their mixtures, which providedyeings having improved fastness properties especially wet- andlight-fastness of dyed polyester or its blends with other fibres andwhich dyes additionally have a high affinity to the fibre that isreflected in good built up properties. About 35 years ago one member ofthis group of compounds, having the following formula:

has been disclosed in Monatshefte für Chemie 111, (1980), p. 529-533 asan intermediate in the production of a compound, which can be used forthe TLC determination of phenols.

The present invention is directed to dyes of formula (I) and mixturesthereof

whereinX is hydrogen or halogen andK is an aromatic or heteroaromatic coupling componentand wherein the dye:

is excluded.

Preferably K is selected from the group consisting of aminobenzene,napht-1-yl, napht-2-yl, quinoline or any other N-heterocyclic fused ringsystem, each of which may be unsubstituted or substituted, and a phenol-or naphthol-radical, each of which may be unsubstituted or substituted.

In general dyes are preferred where X is not hydrogen. However, manypreferred structures exist, where X is hydrogen. Thus in the following,where the preferred embodiments are described in detail e.g. as “X ishydrogen or halogen” or “X is hydrogen, bromo or chloro” such statementrefers to all different subgroups, i.e. the subgroup with X beinghydrogen, the subgroup with X not being hydrogen but anything else andthe subgroup, where X is whatever is mentioned, e.g. halogen.

Preferred are dyes of formula (I), wherein

X is hydrogen or halogen,K is a radical of formula (2)

wherein independent from each otherR¹ is hydrogen, unsubstituted or substituted C₁-C₄-alkyl, unsubstitutedor substituted C₁-C₄-alkoxy, chloro, bromo, benzyloxy or—O—(CH₂)_(n)-A¹-C₁-C₄-alkyl,R² is hydrogen, hydroxyl, unsubstituted or substituted C₁-C₄-alkyl,unsubstituted C₁-C₄-alkoxy, chloro, bromo, acyloxy, acylamino (e.g.NHCO—(CH₂)_(n)-A¹-C₁-C₄-alkyl) or alkylsulfonylamino (e.g.NHSO₂—(CH₂)_(n)-A¹-C₁-C₄-alkyl),

-   -   wherein n is 1 to 4 and A¹ is O, O—CO, O—CO—O or CO—O and        R³ and R⁴ is unsubstituted or substituted C₁-C₄-alkyl,        unsubstituted or substituted phenyl, unsubstituted or        substituted benzyl        or R¹ and R³ together form a 5- or 6-membered aliphatic,        heteroaliphatic, aromatic or heteroaromatic ring,    -   which 5- or 6-membered ring is unsubstituted or substituted.

Dyes, wherein X is hydrogen form one preferred group of dyes. Dyes,wherein X is not hydrogen form another preferred group of dyes. Stillanother preferred group of dyes are those, wherein X is halogen and Bror Cl in particular.

More preferred are dyes of the formula (II)

wherein independent of each otherX is hydrogen, chloro or bromo,R¹ is hydrogen, hydroxyl, C₁-C₄-alkyl, bromo, chloro or C₁-C₄-alkoxy,R² is hydrogen, hydroxyl, carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen,acyloxy, acylamino (e.g. NHCO—C₁-C₄-alkyl, NHCO-aryl, NHCO-benzyl) orsulfonylamino (e.g. NHSO₂—C₁-C₄-alkyl),R³ and R⁴ is hydrogen, C₁-C₄-alkyl, (CH₂)_(n)-phenyl, CH₂—CH═CH₂,(CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl,(CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p) phenyl, CHR²—CH═CH₂, CHR²—(CH₂)_(p)—OH,CHR²—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COOH,CHR²—(CH₂)—COO—(C₁-C₄)-alkyl, CHR²—(CH₂)—COO-phenyl,CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—COO(CH₂)_(p)—(CHR²)_(m)—CO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl,CHR²—(CH₂)_(p)—O—CO-benzyl, CHR²—(CH₂)_(p)-2-furfuryl,COO—CHR²—(CH₂)_(p)-2-dehydropyranyl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-dehydropyranyl,

-   -   whereby all benzyl and phenyl rings can be substituted by        C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano or COOR²        n is 1 to 4,        m is 1 to 4 and        p is 0 to 3.

Even more preferred are dyes of formula (II) wherein independent fromeach other

X is hydrogen, chloro or bromo,R¹ is hydrogen, methyl or methoxy,R² is hydrogen, hydroxy, COOH, COO—C₁-C₂-alkyl, C₁-C₂-alkyl,C₁-C₂-alkoxy, chloro, bromo, —NHCO—C₁-C₂-alkyl, —NHCO-aryl,—NHCO-benzyl, —NHSO₂—C₁-C₂-alkyl or —NHSO₂-aryl,R³ and R⁴ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—CH═CH₂,CHR²—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO-phenyl, CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl orCHR²—(CH₂)_(p)—O—CO-benzyl,n is 1 or 2,m is 1 or 2 andp is 0 or 1.

And most preferred are dyes of the formula (II), wherein independentfrom each other

X is hydrogen, chloro or bromo,R¹ is hydrogen, methyl or methoxy,R² is hydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl, chloro,bromo, —NHCO—(C₁-C₂)-alkyl, —NHSO₂—(C₁-C₂)-alkyl,R³ and R⁴ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(C₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂) alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—O—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—O—CO-phenyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-fururyl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(p)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl, CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkylor CHR²—(CH₂)_(p)—O—CO-phenyl,n is 1 or 2,m is 1 or 2 andp is 0 or 1.

Another preferred embodiment of the present invention are dyes offormula (III)

wherein independent from each otherX is hydrogen, chloro or bromo,R¹ is hydrogen, C₁-C₄-alkyl, bromo, chloro or C₁-C₄-alkoxy,R⁵ is hydrogen or C₁-C₄-alkyl,R³ and R⁴ is hydrogen, C₁-C₄-alkyl, (CH₂)_(n)-phenyl, CH₂—CH═CH₂,(CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl,(CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl CHR²—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)-phenyl, CHR²—CH═CH₂, CHR²—(CH₂)_(p)—OH,CHR²—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COOH,CHR²—(CH₂)_(p)—COO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—COO-phenyl,CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—COO(CH₂)_(p)—(CHR²)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl,CHR²—(CH₂)_(p)—O—CO-benzyl, COO—CHR²—(CH₂)_(p)-2-furfuryl,COO—CHR²—(CH₂)_(p)-2-dehydropyranyl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl orCHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-dehydropyranyl,

-   -   whereby all benzyl and phenyl rings can be substituted by        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, nitro, cyano or COOR²,        n is 1 to 4,        m is 1 to 4 and        p is 0 to 3.

More preferred are dyes of the formula (III), wherein independent fromeach other

X is hydrogen, chloro or bromo,R¹ is hydrogen, methyl or methoxy,R⁵ is methyl or ethyl,R³ and R⁴ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, —(CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—CH═CH₂,CHR²—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO-phenyl, CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl orCHR²—(CH₂)_(p)—O—CO-benzyl,n is 1 or 2,m is 1 or 2 andp is 0 or 1.

Even more preferred are dyes of the formula (III), wherein independentfrom each other

X is hydrogen, chloro or bromo,R¹ is hydrogen, methyl or methoxy,R⁵ is methyl,R³ and R⁴ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—O—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—O—CO-phenyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(p)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl, CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkylor CHR²—(CH₂)—O—CO-phenyl,n is 1 or 2,m is 1 or 2 andp is 0 or 1.

The present invention also provides a process for the production of dyesof formula (I) and mixtures thereof comprising:

a) diazotization of

-   -   wherein X is defined as above and        b) coupling the diazonium salt obtained in step a) with        compounds of formula (2).

The diazotization of the compound of the formula (IV) and (V),respectively can be performed by means of diazotization methods that areknown to a person skilled in the art, preferably by using sodium nitriteor nitrosylsulfuric acid in acidic medium using inorganic acids such ashydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereofor organic acids such as acetic acid or propionic acid or mixturesthereof. Also mixtures of inorganic acid with organic acids can be usedadvantageously.

The coupling reaction of the diazonium salts obtained by diazotizationof the compound of the formula (IV) or (V) onto the compounds offormulae (2) can be performed by known methods.

The compounds of the formula (2) are known and commercially available orcan be synthesised by means of common chemical reactions known to aperson skilled in the art such as the methods disclosed in chemicalencyclopaedia literature like Ullmann's Encylobedia of IndustrialChemistry, Houben-Weyl, other scientific literature and numerouspatents.

Through analogy, all the substances that are used in this invention canbe synthesized as described.

The dyes of the present invention can be used alone or as a mixture withother dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as describedabove is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described aboveforms another preferred aspect of the present invention.

When the dye or a dye mixture of the present invention is used indyeing, the dye/dye mixture is dispersed in an aqueous medium by meansof a dispersing agent and wetting agent in the usual way to prepare adye bath for dyeing or a printing paste for textile printing.

Thus also an aqueous dispersion for dying comprising a dye or dyemixture as described above forms an aspect of the present invention.

Typical examples of dispersing agent are lignosulphonates, naphthalenesulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilicacid/formaldehyde condensates, typical examples of wetting agent arealkyl aryl ethoxylates, which may be sulphonated or phosphated andtypical example of other ingredients, which may be present are inorganicsalts, de-dusting agents such as mineral oil or nonanol, organic liquidsand buffers. Dispersing agents may be present at from 30 to 500% basedon the weight of the dye/dye mixture. Dedusting agents may be used atfrom 0 to 5% based on the weight of the dye/dye mixture.

The dyes and dye-mixtures of the invention are outstandingly suitablefor dyeing and printing hydrophobic materials, the dyeings and printsobtained being notable for level hues and high service fastnesses.Notable features include good wash and contact fastnesses, and alsoexcellent color buildup properties, especially on polyester andpolyester-elastane materials.

Accordingly the present invention also provides for the use of the dyeand dye mixtures of the invention for dyeing and printing hydrophobicmaterials, and provides methods of dyeing or printing such materials inconventional procedures, in which a dye mixture of the invention isemployed as colorant.

The aforementioned hydrophobic materials may be of synthetic orsemisynthetic origin. Suitable materials include, for example, secondarycellulose acetate, cellulose triacetate, polyamides, polylactides, and,in particular, high molecular mass polyesters. Materials made of highmolecular mass polyester are more particularly those based onpolyethylene terephthalates or polytrimethylene terephthalates. Alsocontemplated are blend fabrics and blend fibers such as polyester-cottonor polyester-elastane, for example. The hydrophobic synthetic materialsmay take the form of films or sheet- or threadlike constructions and mayhave been processed, for example, into yarns or into woven or knittedtextile materials. Preference is given to fibrous textile materials,which may also be present in the form of microfibers, for example.

Dyeing in accordance with the use provided by the invention may takeplace in conventional manner, preferably from aqueous dispersion,optionally in the presence of carriers, at between 80 to about 110° C.by the exhaust process or by the HT process in a dyeing autoclave at 110to 140° C., and also by the so-called thermofix process, in which thefabric is padded with the dyeing liquor and subsequently fixed at about180 to 230° C.

Printing of the aforementioned materials may be carried out in a mannerknown per se by incorporating the dye mixtures of the invention in aprint paste and treating the fabric printed therewith to fix the dye,optionally in the presence of a carrier, at temperatures between 180 to230° C., with HT steam, pressurized steam or dry heat.

Suitable process conditions may be selected from the following:

-   (i) exhaust dyeing at a pH of from 4 to 8.5, at a temperature of    from 125 to 140° C. for from 10 to 120 minutes and under a pressure    of from 1 to 2 bar, a sequestrant optionally being added;-   (ii) continuous dyeing at a pH of from 4 to 8.5, at a temperature of    from 190 to 225° C. for from 15 seconds to 5 minutes, a migration    inhibitor optionally being added;-   (iii) direct printing at a pH of from 4 to 6.5, at a temperature of    from 160 to 185° C. for from 4 to 15 minutes for high temperature    steaming, or at a temperature of from 190 to 225° C. for from 15    seconds to 5 minutes for bake fixation with dry heat or at a    temperature of from 120 to 140° C. and 1 to 2 bar for from 10 to 45    minutes for pressure steaming, wetting agents and thickeners (such    as alginates) of from 5 to 100% by weight of the dye optionally    being added;-   (iv) discharge printing (by padding the dye on to the textile    material, drying and overprinting) at a pH of from 4 to 6.5,    migration inhibitors and thickeners optionally being added;-   (v) carrier dyeing at a pH of from 4 to 7.5, at a temperature of    from 95 to 100° C. using a carrier such as methylnaphthalene,    diphenylamine or 2-phenylphenol, sequestrants optionally being    added; and-   (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of    from 4 to 7.5, at a temperature of about 85° C. for acetate or at a    temperature of about 90° C. for triacetate and nylon for from 15 to    90 minutes, sequestrants optionally being added.

For use in dyeing liquors, padding liquors or print pastes, the dyemixtures of the invention are to be in a very fine state of subdivision.Fine subdivision of the dyes is accomplished in a manner known per se byslurrying them together with dispersants in a liquid medium, preferablywater, and subjecting the mixture to the action of shearing forces, thedye particles originally present being mechanically comminuted to anextent such that an optimum specific surface area is attained and thesedimentation of the dye is extremely low. This is done in suitablemills, such as ball or sand mills. The particle size of the dyes isgenerally between 0.1 and 5 μm, preferably about 1 μm.

The dispersants which are used in the milling operation may be nonionicor anionic. Nonionic dispersants are, for example, reaction products ofalkylene oxides, such as ethylene oxide or propylene oxide, withalkylatable compounds, such as fatty alcohols, fatty amines, fattyacids, phenols, alcohol phenols, and carboxamides, for example. Anionicdispersants are, for example, lignosulfonates, alkyl- oralkylarylsulfonates or alkylaryl polyglycol ether sulfates.

For the majority of applications the dye preparations obtained in thisway are to be pourable. In these cases, therefore, there are limits onthe dye content and dispersant content. Generally speaking, thedispersions are adjusted to a dye content of up to 50 percent by weightand a dispersant content of up to about 25 percent by weight. Foreconomic reasons, dye contents are usually not below 15 percent byweight.

The dispersions may also comprise other auxiliaries as well, examplesbeing those which act as oxidizing agents, such as sodiumm-nitrobenzenesulfonate, for example, or fungicidal agents, such assodium o-phenylphenoxide and sodium pentachlorophenoxide, for example,and more particularly what are known as “acid donors”, such asbutyrolactone, monochloroacetamide, sodium chloroacetate, sodiumdichloroacetate, the Na-salt of 3-chloropropionic acid, monoesters ofsulfuric acid such as lauryl sulfate, for example, and also sulfuricesters of ethoxylated and propoxylated alcohols, such as butylglycolsulfate, for example.

The dye dispersions obtained in this way can be used with greatadvantage for making up dyeing liquors and print pastes.

There are certain fields of use where powder formulations are preferred.These powders comprise the dye, dispersants, and other auxiliaries, suchas wetting, oxidizing, preserving, and dust proofing agents, forexample, and the abovementioned “acid donors”.

One preferred method of producing dye preparations in powder forminvolves stripping the liquid from the liquid dye dispersions describedabove, by means, for example, of vacuum drying, freeze drying, or bydrying on drum dryers, but preferably by spray drying.

The dyeing liquors are produced by diluting the required amounts of theabove-described dye formulations with the dyeing medium, preferably withwater, to an extent such as to give a liquor ratio of 5:1 to 50:1 fordyeing. Additionally the liquors are generally admixed with furtherdyeing auxiliaries, such as dispersants, wetting agents, and fixingauxiliaries. Organic and inorganic acids such as acetic acid, succinicacid, boric acid or phosphoric acid are added to set a pH of 4 to 5,preferably 4.5. It is advantageous to buffer the pH which has been setand to add a sufficient amount of a buffer system. One advantageousbuffer system, for example, is the acetic acid/sodium acetate system.

Where the dye mixture is to be used in textile printing, the requiredamounts of the abovementioned dye formulations are kneaded inconventional manner together with thickeners, such as alkali metalalginates or the like, for example, and, optionally, with furtheradjuvants, such as fixation accelerants, wetting agents, and oxidizingagents, for example, to form print pastes.

The present invention also provides inks for digital textile printing bythe ink jet process, which comprise a dye mixture of the invention.

The inks of the invention are preferably aqueous and comprise dyemixtures of the invention in amounts, for example, of 0.1% to 50% byweight, preferably in amounts of 1% to 30% by weight, and morepreferably in amounts of 1% to 15% by weight, based on the total weightof the ink. In addition they comprise in particular from 0.1% to 20% byweight of a dispersant. Suitable dispersants are known to a personskilled in the art, are available commercially, and include, forexample, sulfonated or sulfomethylated lignins, condensation products ofaromatic sulfonic acids and formaldehyde, condensation products ofsubstituted or unsubstituted phenol and formaldehyde, polyacrylates andcorresponding copolymers, modified polyurethanes, and reaction productsof alkylene oxides with alkylatable compounds, such as fatty alcohols,fatty amines, fatty acids, carboxamides, and unsubstituted orsubstituted phenols, for example.

The inks of the invention may further comprise the usual additives,examples being viscosity moderators to set viscosities in the range from1.5 to 40.0 mPas in a temperature range from 20 to 50° C. Preferred inkshave a viscosity of 1.5 to 20 mPas, and particularly preferred inks aviscosity of 1.5 to 15 mPas.

Suitable viscosity moderators include rheological additives, such aspolyvinylcaprolactam, polyvinylpyrrolidone, and their copolymers,polyether polyol, associative thickeners, polyurea, sodium alginates,modified galactomannans, polyetherurea, polyurethane, and nonioniccellulose ethers, for example.

The inks may further comprise customary adjuvants, such as substancesfor inhibiting fungal and bacterial growth, for example, in amounts of0.01% to 1% by weight, based on the total weight of the ink.

An overview of such suitable printing- or formulation aids is given ingreater detail e.g. in EP 1 735 385.

In contrast to conventional textile printing, where the printing inkalready contains all necessary chemicals, in digital or inkjet printingthe auxiliaries have to be applied to the textile substrate in aseparate pretreatment step.

The dyestuff may also be applied to textile materials usingsupercritical carbon dioxide, in which case the dye formulating agentsmay optionally be omitted.

The synthetic textile material may preferably be selected from aromaticpolyester, especially polyethylene terephthalate, polyamide, especiallypolyhexamethylene adipamide. Also secondary cellulose acetate, cellulosetriacetate, and natural textile materials, especially cellulosicmaterials and wool may be selected. An especially preferred textilematerial is an aromatic polyester or fibre blend thereof with fibres ofany of the mentioned textile materials. Especially preferred fibreblends include those of polyester-cellulose, such as polyester-cotton,and polyester-wool. The textile materials or blends thereof may be inthe form of filaments, loose fibres, yarn or woven or knitted fabrics.

Particularly, among polyester fibres, not only ordinary polyester fibres(regular denier fibres) but also microfibers (fine denier fibres, whichare less than 0.6 denier) may be used as fibres which can successfullybe dyed with the dye mixture of the present invention.

In general all kinds of fibers can be dyed and therefore fiber andblends containing such fiber selected from the group consisting of:synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 andaramid fibres, vegetable fibres, seed fibres, cotton, organic cotton,kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf,ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres,bamboo; fibres from animals, wool, organic wool, silk, cashmere wool,alpaca fiber, mohair, Angora fibre as well as fur and leather materials;manufactured, regenerated and recycled fibres, cellulosic fibres; paperfibres, cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers, and Lyocell fibers comprising a dye mixture asdescribed above either in chemically and/or physically bound formforms/form another aspect of the present invention.

The examples below serve to illustrate the invention. Parts andpercentages are by weigh unless noted otherwise. The relationshipbetween parts by weight and parts by volume is that of the kilogram tothe liter.

EXAMPLES Intermediate 1:

192 ml (2 Mol) of m 3-Fluor-aniline are added to 200 ml of Toluidine andstirred. To this mixture is heated to 50° C. and 203 ml (2.1 Mol) ofAcetanhydride are added while the temperature is kept at 50 to 60° C.After 2 h the mixture is evaporated under vacuum. The remaining productis mixed with 1000 ml of cold water filtrated and dried under vacuum,conditions delivering 292 g of intermediate 1

Intermediate 2:

137.9 g (0.9 Mol) of Intermediate 1 are added slowly to a mixture of 259g HNO₃ and 630 g of H₂SO₄ at −5 to 0° C. The mixture is stirred at 0 to5° C. for 1 h and then added to a stirred mix of 4 l ice/water, isolatedby filtration and dried under vacuum conditions to deliver 140 g ofIntermediate 2

Intermediate 3:

140 g of intermediate 2 are added to 545 ml 50% H₂SO₄ and heated for 3 hto 100° C. under stirring. The mixture is added to 5 l of ice/water,isolated by filtration and dried under vacuum conditions to deliver 107g of intermediate 3

An alternative synthesis for intermediate 3 is shown below: (OrganicLetters, 14(10), 2504-2507; 2012/Journal of Organic Chemistry, 27,1910-11; 1962/Bioorganic & Medicinal Chemistry Letters, 21(14),4189-4192; 2011)

Intermediate 4:

38.8 g (0.193 Mol) of Intermediate 3 are dissolved in 200 ml of aceticacid and 40 ml of 37% HCl are added. The mixture is stirred at 25° C.and 21 ml of H₂O₂ 35% are added slowly. This mixture is stirred at 25 to30° C. for 3 days and then poured on 1000 ml of ice/water, isolated byfiltration and dried under vacuum conditions to deliver 39.5 g ofintermediate 4

Intermediate 5:

38.8 g (0.193 Mol) of Intermediate 3 are dissolved in 200 ml of aceticacid and 11.6 ml Bromine (0.22 Mol) are added slowly at 25° C. Thismixture is stirred at for 3 days at 25 to 30° C. and then the poured on1000 ml of ice/water, isolated by filtration and dried under vacuumconditions to deliver 48.1 g of intermediate 5

Coupling Components (K)/(2) and (2a)

for disperse dyes are well known and described in chemical encyclopaedialiterature like Ullmann's Encylobedia of Industrial Chemistry,Houben-Weyl, other scientific literature and numerous patents. Thusdetailed synthesis is only given for a few coupling components.

Coupler 1:

80 g of Zn powder are activated by stirring it in 5% aqueous HCl,filtrated and washed with water. 54 g (0.3 Mol) of3-Amino-4-methoxyacetanilid are stirred in 250 ml of acetic acid and 25ml of water and 35.2 g (0.3 Mol) of Methyacetoacetat (CH₃COCH₂COOCH₃).To this mixture the activated Zn-powder is added at 25° C. Thetemperature rises after the reaction starts and is kept at 80 to 90° C.for 12 h. The acetic acid is evaporated under vacuum and 300 ml waterand 300 ml CH₂Cl₂ are added. The pH is adjusted to 7 with Ammoniasolution and the 2 phases are mixed intensively, after phase-separation,the organic phase is isolated.

The aqueous phase is extracted with 100 ml of CH₂Cl₂ and both organicphases are combined, washed with water, dried with MgSO₄ and evaporatedunder vacuum resulting in 39.2 g of Coupler 1

Dye Example 1 Diazotation:

8.8 g of intermediate 3 are mixed with 85 ml of acetic-/propionic-acid(60/40) and cooled down to 0° C. 8.0 ml of nitrosylsulfuric acid isadded slowly at 0° C. This mixture is stirred 4 h at 0° C. and theexcess of Nitrite is destroyed the Amidosulfonic acid.

Coupling:

9.4 g of 3-(N,N-diethyl)-aminoacetanilid are mixed with 140 ml ofMethanol and 10 g of Sodium acetate and 2 g of urea and cooled down to5° C. To this mixture the diazotation is added slowly and the reactionmixture is stirred for 30 min at 5° C.

100 ml of water are added and the resulting product is isolated byfiltration.

After re-crystallisation from Ethanol and drying under vacuumconditions, 10.6 g of the dye are obtained.

This dye of the invention was further formulated using dispersing agent,glass bead milling and dried via spray drying and gives deep violetdyeing's or prints, on polyester or polyester blends for example, underthe dyeing conditions typical for disperse dyes with very good fastnessproperties.

Example 2 Diazotation:

8.8 g of intermediate 5 are mixed with 85 ml of acetic-/propionic-acid(60/40) and cooled down to 0° C. 8.0 ml of nitrosylsulfuric acid isadded slowly at 0° C. This mixture is stirred 4 h at 0° C. and theexcess of Nitrite is destroyed the Amidosulfonic acid.

Coupling:

11.04 g of 3-(N,N-dipropyl)mesylmetamin(N-(3-Dipropylamino-phenyl)metanesulfonamid) are mixed with 140 ml ofMethanol and 10 g of Sodium acetate and 2 g of urea and cooled down to5° C. To this mixture the diazotation is added slowly and the reactionmixture is stirred for 30 min at 5° C.

100 ml of water are added and the resulting product is isolated byfiltration.

After re-crystallisation from Acetone and drying under vacuumconditions, 10.6 g of the Example 2-dye are obtained.

The resulting dye of the invention was formulated using dispersingagent, glass bead milling and dried via spray drying and gives deepviolet dyeing's or prints on polyester or polyester blends for example,under the dyeing conditions typical for disperse dyes with very goodfastness properties.

Examples 3 to 5

With the following annelated/substituted couplers (Coupler 2 to 4) andthe diazo-component Intermediate 3 or Intermediate 5 also high wash fastdyes can be prepared following the procedure of Example 1.

that dyes polyester in deep red shades,

that dyes polyester in deep reddish blue shades,

that dyes polyester in deep bluish-red shades.

Examples 6 to 63 of Formula (IIa)

can be prepared according the procedure of example 1 or 2using Intermediate 3 as a diazo-component and coupling components offormula (2) with:

Shade on No: R¹ R² R³ R⁴ polyester 6 Hydrogen CH₃ (CH₂)₂—O—CH₃(CH₂)₂—O—CH₃ Red-violet 7 Hydrogen CH₃ (CH₂)₂—COO—CH₃ HydrogenRed-violet 8 Hydrogen CH₃ C₂H₄ (CH₂)₂—COO—CH₃ Red-violet 9 HydrogenHydrogen C₂H₄ CH₂—COO—CH₃ Red-violet 10 Hydrogen Hydrogen (CH₂)₂—COO—CH₃(CH₂)₂—COO—CH₃ Bluish red 11 Hydrogen Hydrogen (CH₂)₂—COO—CH₃ C₂H₄Red-violet 12 Hydrogen Hydrogen CH₂-phenyl CH₂—CH═CH₂ Red-violet 13Hydrogen Hydrogen CH₂—CH═CH₂ CH₂—CH═CH₂ Red-violet 14 HydrogenCOO(CH₂)₂—O—CH₃ C₂H₅ C₂H₅ Bluish red 15 Hydrogen COO(CH₂)₂—O—CH₃Hydrogen CH₂-phenyl Bluish red 16 Hydrogen Hydrogen (CH₂)₂—O—CH₃(CH₂)₂—O—CH₃ Red-violet 17 Hydrogen Hydrogen Hydrogen (CH₂)₂—O—C₂H₅Bluish red 18 Hydrogen Hydrogen (CH₂)₂—O-phenyl (CH₂)₂—O-phenylRed-violet 19 Hydrogen Hydrogen (CH₂)₂—O-benzyl CH₃ Red-violet 20Hydrogen Hydrogen CH₂-phenyl CH₂—COO—CH₃ Red-violet 21 Hydrogen ClHydrogen (CH₂)₂—O—CH₃ Red 22 Hydrogen Cl CH₂—COO—C₂H₅ CH₂—COO—C₂H₅Red-violet 23 Hydrogen Cl (CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃ Bluish red 24Hydrogen Hydrogen (CH₂)₂—COO—CH₃ CH₂-phenyl Red-violet 25 HydrogenHydrogen (CH₂)₂—COO—CH₃ Hydrogen Bluish red 26 Hydrogen Hydrogen(CH₂)₂—COO-phenyl Hydrogen Bluish red 27 Hydrogen Hydrogen CH₃(CH₂)₂—COO-benzyl Red-violet 28 Hydrogen Hydrogen (CH₂)₂—CN(CH₂)₂—COO-benzyl Red-violet 29 Hydrogen Hydrogen (CH₂)₂—CN (CH₂)₂—CNBluish red 30 Hydrogen Hydrogen (CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenylRed-violet 31 Hydrogen Hydrogen Hydrogen (CH₂)₂—COO—CH₂—CO—CH₃ Bluishred 32 Hydrogen Hydrogen (CH₂)₂—COO—CH₂—CO-phenyl C₂H₅ Red-violet 33Hydrogen COOH CH₂—CH═CH₂ CH₂—CH═CH₂ Bluish red 34 Hydrogen COOH CH₃ CH₃Bluish red 35 Hydrogen COOH C₂H₅ (CH₂)₂—OCO-phenyl Bluish red 36Hydrogen Hydrogen (CH₂)₂—OCO-phenyl C₂H₄ Red-violet 37 Hydrogen Hydrogen(CH₂)₂—O—CH₂-(2-furfuryl) C₂H₄ Red-violet 38 Hydrogen Hydrogen(CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₂-(2-furfuryl) Red-violet 39 HydrogenHydrogen Hydrogen CH(CH₃)—CH₂—COO—CH₃ Bluish red 40 Hydrogen HydrogenCH(CH₃)—CH₂—COO—CH₂—CO—CH₃ CH₂-phenyl Red-violet 41 Hydrogen HydrogenHydrogen CH(CH₃)—CH₂—COO—CH₂—CO-phenyl Bluish red 42 Hydrogen HydrogenCH(CH₃)—CH₂—OCO—CH₃ Hydrogen Bluish red 43 Hydrogen Hydrogen HydrogenCH(CH₃)—CH₂—OCO-phenyl Bluish red 44 Hydrogen Hydrogen C₂H₄ CH₂-phenylRed-violet 45 Hydrogen Hydrogen Hydrogen CH₂-phenyl Violet 46 HydrogenHydrogen C₂H₄ C₂H₄ Red-violet 47 Hydrogen CH₃ CH₂—COO—C₂H₅ CH₂—COO—C₂H₅Red-violet 48 Hydrogen CH₃ CH₂—COO—CH₃ Hydrogen Red-violet 49 HydrogenCH₃ C₂H₄ (CH₂)₂—OCO—CH₃ Red-violet 50 Hydrogen CH₃ (CH₂)₂—COO—CH₂—CO—CH₃C₂H₅ Red-violet 51 Hydrogen CH₃ Hydrogen CH₂-phenyl Red-violet 52Hydrogen CH₃ CH₂-phenyl (CH₂)₂—COO—CH₂—CO—CH₃ Red-violet 53 Hydrogen CH₃CH(CH₃)—CH₂—OCO—CH₃ Hydrogen Red-violet 54 Hydrogen Hydrogen(CH₂)₂—OCO—CH₃ (CH₂)₂—OCO—CH₃ Red-violet 55 Hydrogen Hydrogen(CH₂)₂—OCO—CH₃ C₂H₄ Red-violet 56 Hydrogen Hydrogen Hydrogen(CH₂)₂—OCO—CH₃ Bluish red 57 Hydrogen COOCH₃ (CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃Bluish red 58 Hydrogen COOCH₃ (CH₂)₂—COO—CH₃ Hydrogen Bluish red 60Hydrogen COOCH₃ CH₂-phenyl C₂H₅ Bluish red 61 Hydrogen OH C₂H₅ C₂H₅Violet 62 Hydrogen OH CH₂-phenyl C₂H₅ Violet 63 Hydrogen OH(CH₂)₂—O—C₂H₅ (CH₂)₂—O—C₂H₅ Violet

Examples 64 to 95 of Formula (IIb)

can be prepared according the procedure of example 1 or 2using Intermediate 4 or intermediate 5 as a diazo-component and couplingcomponents of formula (2) with:

Shade on No: X R¹ R² R³ R⁴ polyester 64 Cl Hydrogen Hydrogen CH₃ CH₃Violet 65 Br Hydrogen Hydrogen CH₂—CH═CH₂ CH₂—CH═CH₂ Violet 66 BrHydrogen Hydrogen (CH₂)₂—O—C₂H₅ (CH₂)₂—O—C₂H₅ Violet 67 Br HydrogenHydrogen CH₂—COO—CH₃ Hydrogen Red-violet 68 Br Hydrogen HydrogenCH₂—COO—C₂H₅ CH₂-phenyl Red-violet 69 Br Hydrogen Hydrogen C₄H₉CH₂—COO—C₂H₅ Red-violet 70 Br Hydrogen Hydrogen (CH₂)₂—COO—C₂H₅(CH₂)₂—COO—C₂H₅ Red-violet 71 Br Hydrogen Hydrogen C₂H₄ (CH₂)₂—COO—CH₃Violet 72 Cl Hydrogen Hydrogen (CH₂)₂—COO—CH₃ CH₂-phenyl Violet 73 ClHydrogen Hydrogen (CH₂)₂—COO—CH₃ Hydrogen Red-violet 74 Br HydrogenHydrogen Hydrogen (CH₂)₂—COO-phenyl Red-violet 75 Br Hydrogen Hydrogen(CH₂)₂—CN (CH₂)₂—CN Red-violet 76 Br Hydrogen Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ C₂H₅ Violet 78 Cl Hydrogen Hydrogen CH₂—phenyl(CH₂)—COO—CH₂—CO—CH₃ Red-violet 79 Cl Hydrogen Hydrogen Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ Red-violet 80 Br Hydrogen Hydrogen (CH₂)₂—OCO—CH₃(CH2)₂—OCO—CH₃ Red-violet 81 Br Hydrogen Hydrogen C₂H₄ (CH₂)₂—OCO—CH₃Violet 82 Cl Hydrogen Hydrogen (CH₂)₂—OCO—CH₃ CH₂-phenyl Violet 83 ClHydrogen Hydrogen (CH₂)₂—OCO—CH₃ Hydrogen Red-violet 84 Cl Hydrogen CH₃(CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃ Violet 85 Br Hydrogen CH₃ Hydrogen(CH₂)₂—COO—CH₃ Red-violet 86 Br Hydrogen CH₃ (CH₂)₂—COO—C₂H₅(CH₂)₂—COO—C₂H₅ Red-violet 87 Br Hydrogen CH₃ C₂H₄ (CH₂)₂—COO—CH₃ Violet88 Br Hydrogen CH₃ (CH₂)₂—COO—CH₃ CH₂-phenyl Violet 89 Br Hydrogen CH₃(CH₂)₂—COO—CH₂—CO—CH₃ C₂H₅ Red-violet 90 Br Hydrogen CH₃(CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenyl Violet 91 Br Hydrogen CH₃CH(CH₃)—CH₂—OCO—C₂H₅ Hydrogen Red-violet 92 Br Hydrogen Cl CH₂—COO—CH₃CH₂—COO—CH₃ Red-violet 93 Cl Hydrogen COOCH₃ (CH₂)₂—COO—C₂H₅ HydrogenRed-violet 94 Cl Hydrogen COOH C₃H₇ C₃H₇ Red-violet 95 Cl Hydrogen OH(CH₂)₂—O—C₂H₅ (CH₂)₂—O—C₂H₅ Red-violet

Examples 96 to 202 of Formula (IIc)

i. e. structures, wherein R² of general structure (II) is NHCO—R⁵, and

-   -   wherein the R⁵ is alkyl, i. e. R² of (II) is NHCO—(C₁-C₂)-alkyl        and which        can be prepared according the procedure of example 1 or 2        using Intermediate 3 as a diazo-component and coupling        components of formula (2a) with:

Shade on No: R¹ R³ R⁴ R⁵ polyester 96 Hydrogen (CH₂)₂—O—(CH₂)₃—O—CH₃(CH₂)₂—O—(CH₂)₃—O—CH₃ Methyl Violet 97 Hydrogen CH₂—COO—CH₃ CH₂—COO—CH₃Methyl Violet 98 Hydrogen CH₂-phenyl CH₂—COO—CH₃ Methyl Violet 99Hydrogen C₂H₄ CH₂—COO—CH₃ Methyl Violet 100 Hydrogen (CH₂)₂—COO—CH₃(CH₂)₂—COO—CH₃ Methyl Violet 101 Hydrogen (CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃Methyl Violet 102 Hydrogen Hydrogen (CH₂)₂—O—C₂H₅ Ethyl Violet 103Hydrogen (CH₂)₂—O-phenyl (CH₂)₂—O-phenyl Methyl Violet 104 Hydrogen C₂H₄(CH₂)₂—O-phenyl Methyl Violet 105 Hydrogen (CH₂)₂—O-benzyl HydrogenMethyl Violet 106 Hydrogen CH(CH₃)—CH₂—COO—CH₂—CO—CH₃ Hydrogen MethylViolet 107 Hydrogen Hydrogen CH(CH₃)—CH₂—COO—CH₂—CO-phenyl Methyl Violet108 Hydrogen CH(CH₃)—CH₂—OCO—CH₃ Hydrogen Methyl Violet 109 HydrogenCH(CH₃)—CH₂—OCO—C₂H₅ C₂H₄ Ethyl Violet 110 Hydrogen HydrogenCH(CH₃)—CH₂—OCO-phenyl Methyl Violet 111 Hydrogen (CH₂)₂—COO—CH₃ C₂H₄Methyl Violet 112 Hydrogen (CH₂)₂—COO—CH₃ CH₂-phenyl Methyl Violet 113Hydrogen (CH₂)₂—COO—CH₃ Hydrogen Methyl Violet 114 Hydrogen(CH₂)₂—COO-phenyl Hydrogen Ethyl Violet 115 Hydrogen HydrogenCH₂)₂—COO-benzyl Methyl Violet 116 Hydrogen (CH₂)₂—O—CH₂-(2-furfuryl)C₂H₄ Methyl Violet 117 Hydrogen CH₂—COO—CH₂-(2-furfuryl) CH₂—COO—C₂H₅Ethyl Violet 118 Hydrogen (CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₂-(2-furfuryl)Methyl Violet 119 Hydrogen Hydrogen CH(CH₃)—CH₂—COO—CH₃ Methyl Violet120 Hydrogen CH(CH₃)—CH₂—O—CH₃ Hydrogen Methyl Violet 121 HydrogenHydrogen (CH₂)₂—COO—CH₂—CO-phenyl Methyl Violet 122 Hydrogen(CH₂)₂—OCO—CH₃ (CH₂)₂—OCO—CH₃ Methyl Violet 123 Hydrogen (CH₂)₂—OCO—CH₃CH₂-phenyl Methyl Violet 124 Hydrogen Hydrogen (CH₂)₂—OCO—CH₃ MethylViolet 125 Hydrogen (CH₂)₂—OCO-phenyl Hydrogen Ethyl Violet 126 Hydrogen(CH₂)₂—OCO-phenyl C₂H₄ Methyl Violet 127 Hydrogen (CH₂)₂—CN (CH₂)₂—CNMethyl Violet 128 Hydrogen Hydrogen (CH₂)₂—CN Ethyl Violet 129 Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ C₂H₅ Methyl Violet 130 Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenyl Methyl Violet 131 Hydrogen Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ Methyl Violet 132 Hydrogen C₂H₄ CH₂-phenyl MethylViolet 133 Hydrogen Hydrogen CH₂-phenyl Methyl Violet 134 HydrogenHydrogen CH₃ Ethyl Violet 135 Hydrogen C₃H₇ C₃H₇ Ethyl Violet 136Hydrogen CH₂—CH═CH₂ CH₂—CH═CH₂ Methyl Violet 137 Methoxy C₂H₄ CH₂-phenylMethyl Blue 138 Methoxy Hydrogen CH₂-phenyl Ethyl Blue 139 MethoxyHydrogen CH₃ Methyl Blue 140 Methoxy C₂H₄ C₂H₄ Methyl Blue 141 EthoxyCH₂-phenyl CH₂—CH═CH₂ Methyl Blue 142 Methoxy CH₂—CH═CH₂ CH₂—CH═CH₂Methyl Blue 143 Methoxy (CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃ Methyl Blue 144Methoxy (CH₂)₂—O—C₂H₅ CH₂)₂—O—C₂H₅ Ethyl Blue 145 Ethoxy Hydrogen(CH₂)₂—O—C₂H₅ Methyl Blue 146 Methoxy (CH₂)₂—O-phenyl (CH₂)₂—O-phenylMethyl Blue 147 Methoxy C₂H₄ (CH₂)₂—O-phenyl Methyl Blue 148 MethoxyHydrogen (CH₂)₂—O-phenyl Ethyl Blue 149 Methoxy (CH₂)₂—O-benzyl(CH₂)₂—O-benzyl Methyl Blue 150 Ethoxy (CH₂)₂—O-benzyl CH₃ Ethyl Blue151 Methoxy (CH₂)₂—O-benzyl Hydrogen Methyl Blue 152 Methoxy(CH₂)₂—O—(CH₂)₃—O—CH₃ (CH₂)₂—O—(CH₂)₃—O—CH₃ Methyl Blue 153 Ethoxy(CH₂)₂—O—(CH₂)₃—O—C₂H₅ (CH₂)₂—O—(CH₂)₃—O—C₂H₅ Methyl Blue 154 MethoxyCH₂—COO—CH₃ CH₂—COO—CH₃ Methyl Blue 155 Methoxy CH₂-phenyl CH₂—COO—CH₃Ethyl Blue 156 Methoxy C₂H₄ CH₂—COO—CH₃ Methyl Blue 157 MethoxyCH₂—COO—C₂H₅ CH₂—COO—C₂H₅ Methyl Blue 158 Methoxy (CH₂)₂—COO—CH₃(CH₂)₂—COO—CH₃ Methyl Blue 159 Ethoxy (CH₂)₂—COO—C₂H₅ (CH₂)₂—COO—C₂H₅Methyl Blue 160 Methoxy (CH₂)₂—COO—CH₃ C₂H₄ Methyl Blue 161 Methoxy(CH₂)₂—COO—CH₃ CH₂-phenyl Methyl Blue 162 Ethoxy CH₃ (CH₂)₂—COO—C₂H₅Methyl Blue 163 Methoxy Hydrogen (CH₂)₂—COO—CH₃ Methyl Blue 164 Methoxy(CH₂)₂—COO-phenyl Hydrogen Ethyl Blue 165 Methoxy (CH₂)₂—COO-phenyl C₂H₄Methyl Blue 166 Ethoxy (CH₂)₂—COO-phenyl (CH₂)₂—O—CH₃ Methyl Blue 167Methoxy (CH₂)₂—COO-phenyl CH₂-phenyl Methyl Blue 168 Methoxy Hydrogen(CH₂)₂—COO-benzyl Methyl Blue 169 Methoxy CH₃ (CH₂)₂—COO-benzyl EthylBlue 170 Methoxy (CH₂)₂—CN (CH₂)₂—COO-benzyl Methyl Blue 171 Methoxy(CH₂)₂—CN (CH₂)₂—CN Methyl Blue 172 Methoxy Hydrogen (CH₂)₂—CN EthylBlue 173 Methoxy (CH₂)₂—COO—CH₂—CO—CH₃ C₂H₅ Methyl Blue 174 Methoxy(CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenyl Methyl Blue 175 Methoxy Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ Methyl Blue 176 Methoxy (CH₂)₂—COO—CH₂—CO—C₂H₅ CH₃Methyl Blue 177 Methoxy (CH₂)₂—COO—CH₂—CO-phenyl C₂H₅ Methyl Blue 178Methoxy Hydrogen (CH₂)₂—COO—CH₂—CO-phenyl Methyl Blue 179 Ethoxy(CH₂)₂—COO—CH₂—CO-benzyl C₂H₅ Methyl Blue 180 Methoxy Hydrogen(CH₂)₂—COO—CH₂—CO-benzyl Methyl Blue 181 Methoxy (CH₂)₂—OCO—CH₃(CH₂)₂—OCO—CH₃ Methyl Blue 182 Methoxy (CH₂)₂—OCO—C₂H₅ (CH₂)₂—OCO—C₂H₅Methyl Blue 183 Methoxy (CH₂)₂—OCO—CH₃ C₂H₄ Methyl Blue 184 Methoxy(CH₂)₂—OCO—CH₃ CH₂-phenyl Methyl Blue 185 Ethoxy Hydrogen (CH₂)₂—OCO—CH₃Ethyl Blue 186 Methoxy (CH₂)₂—OCO-phenyl Hydrogen Methyl Blue 187Methoxy (CH₂)₂—OCO-phenyl C₂H₄ Methyl Blue 188 Methoxy (CH₂)₂—OCO-phenyl(CH₂)₂—O—CH₃ Methyl Blue 189 Methoxy (CH₂)₂—O—CH₂-(2-furfuryl)CH₂-phenyl Methyl Blue 190 Methoxy (CH₂)₂—O—CH₂-(2-furfuryl) C₂H₄ MethylBlue 191 Methoxy (CH₂)₂—O—CH₂-(2-furfuryl) (CH₂)₂—COO—C₂H₅ Methyl Blue192 Methoxy CH₂—COO—CH₂-(2-furfuryl) CH₂—COO—C₂H₅ Methyl Blue 193Methoxy (CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₂-(2-furfuryl) Methyl Blue 194Methoxy Hydrogen CH(CH₃)—CH₂—COO—CH₃ Methyl Blue 195 MethoxyCH(CH₃)—CH₂—O—CH₃ Hydrogen Methyl Blue 196 Methoxy HydrogenCH(CH₃)—CH₂—O—C₂H₅ Methyl Blue 197 Methoxy CH(CH₃)—CH₂—COO—CH₂—CO—CH₃Hydrogen Methyl Blue 198 Methoxy CH(CH₃)—CH₂—COO—CH₂—CO—CH₃ CH₂-phenylEthyl Blue 199 Methoxy Hydrogen CH(CH₃)—CH₂—COO—CH₂—CO-phenyl MethylBlue 200 Methoxy CH(CH₃)—CH₂—OCO—CH₃ Hydrogen Methyl Blue 201 MethoxyCH(CH₃)—CH₂—OCO—C₂H₅ C₂H₄ Methyl Blue 202 Methoxy HydrogenCH(CH₃)—CH₂—OCO-phenyl Methyl Blue

Examples 203 to 312 of Formula (III)

can be prepared according the procedure of example 1 or 2using Intermediate 4 or Intermediate 5 as a diazo-component and couplingcomponents of formula (2a) with:

Shade on No: X R¹ R³ R⁴ R⁵ polyester 203 Bromo Hydrogen(CH₂)₂—O—(CH₂)₃—O—CH₃ (CH₂)₂—O—(CH₂)₃—O—CH₃ Methyl Blue 204 ChloroHydrogen CH₂—COO—CH₃ CH₂—COO—CH₃ Methyl Reddish blue 205 Bromo HydrogenC₂H₄ CH(CH₃)—COO—C₂H₅ Methyl Blue 206 Bromo Hydrogen CH(CH₃)—COO—CH₃CH₂—COO—CH₃ Methyl Reddish blue 207 Bromo Hydrogen (CH₂)₂—COO—CH₃(CH₂)₂—COO—CH₃ Methyl Reddish blue 208 Bromo Hydrogen (CH₂)₂—O—CH₃(CH₂)₂—O—CH₃ Methyl Blue 209 Chloro Hydrogen Hydrogen (CH₂)₂—O—C₂H₅Ethyl Blue 210 Chloro Hydrogen (CH₂)₂—O-phenyl (CH₂)₂—O-phenyl MethylReddish blue 211 Bromo Hydrogen C₂H₄ (CH₂)₂—O-phenyl Methyl Blue 212Bromo Hydrogen (CH₂)₂—O-benzyl Hydrogen Methyl Reddish blue 213 BromoHydrogen CH(CH₃)—CH₂—COO—CH₂—CO—CH₃ Hydrogen Methyl Reddish blue 214Chloro Hydrogen Hydrogen CH(CH₃)—CH₂—COO—CH₂—CO-phenyl Methyl Reddishblue 215 Bromo Hydrogen CH(CH₃)—CH₂—OCO—CH₃ Hydrogen Methyl Reddish blue216 Bromo Hydrogen CH(CH₃)—CH₂—OCO—C₂H₅ C₂H₄ Ethyl Blue 217 BromoHydrogen Hydrogen CH(CH₃)—CH₂—OCO-phenyl Methyl Reddish blue 218 BromoHydrogen (CH₂)₂—COO—CH₃ C₂H₄ Methyl Blue 219 Bromo Hydrogen(CH₂)₂—COO—CH₃ CH₂-phenyl Methyl Blue 220 Bromo Hydrogen (CH₂)₂—COO—CH₃Hydrogen Methyl Reddish blue 221 Chloro Hydrogen (CH₂)₂—COO-phenylHydrogen Ethyl Reddish blue 222 Chloro Hydrogen Hydrogen(CH₂)₂—COO-benzyl Methyl Blue 223 Bromo Hydrogen(CH₂)₂—O—CH₂—(2-furfuryl) C₂H₄ Methyl Blue 224 Bromo HydrogenCH₂—COO—CH₂—(2-furfuryl) CH₂—COO—C₂H₅ Ethyl Reddish blue 225 ChloroHydrogen (CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₂—(2-furfuryl) Methyl Reddish blue226 Bromo Hydrogen Hydrogen CH(CH₃)—CH₂—COO—CH₃ Methyl Blue 227 BromoHydrogen CH(CH₃)—CH₂—OCH₃ Hydrogen Methyl Reddish blue 228 BromoHydrogen Hydrogen (CH₂)₂—COO—CH₂—CO-phenyl Methyl Reddish blue 229 BromoHydrogen (CH₂)₂—OCO—CH₃ (CH₂)₂—OCO—CH₃ Methyl Reddish blue 230 BromoHydrogen (CH₂)₂—OCO—CH₃ CH₂-phenyl Methyl Blue 231 Chloro HydrogenHydrogen (CH₂)₂—OCO—CH₃ Methyl Blue 232 Bromo Hydrogen (CH₂)₂—OCO-phenylHydrogen Ethyl Reddish blue 234 Bromo Hydrogen (CH₂)₂—OCO-phenyl C₂H₄Methyl Blue 235 Bromo Hydrogen (CH₂)₂—CN (CH₂)₂—CN Methyl Reddish blue236 Chloro Hydrogen Hydrogen (CH₂)₂—CN Ethyl Reddish blue 237 BromoHydrogen (CH₂)₂—COO—CH₂—CO-phenyl C₂H₅ Methyl Blue 238 Bromo Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenyl Methyl Blue 239 Bromo Hydrogen Hydrogen(CH₂)₂—COO—CH₂—CO—CH₃ Methyl Reddish blue 240 Bromo Hydrogen C₂H₄CH₂-phenyl Methyl Blue 241 Chloro Hydrogen Hydrogen CH₂-phenyl MethylReddish blue 242 Bromo Hydrogen Hydrogen CH₃ Ethyl Reddish blue 243Bromo Hydrogen C₂H₄ C₂H₄ Methyl Blue 244 Bromo Hydrogen CH₂—CH═CH₂CH₂—CH═CH₂ Methyl Blue 245 Bromo Methoxy C₂H₄ CH₂-phenyl Methyl Greenishblue 246 Bromo Methoxy Hydrogen CH₂-phenyl Ethyl Blue 247 Bromo MethoxyHydrogen CH₃ Methyl Blue 248 Bromo Methoxy C₂H₄ C₂H₄ Methyl Greenishblue 249 Bromo Ethoxy CH₂-phenyl CH₂—CH═CH₂ Methyl Greenish blue 250Bromo Methoxy CH₂—CH═CH₂ CH₂—CH═CH₂ Methyl Greenish blue 251 BromoMethoxy (CH₂)₂—O—CH₃ (CH₂)₂—O—CH₃ Methyl Greenish blue 252 Bromo Methoxy(CH₂)₂—O—C₂H₅ (CH₂)₂—O—C₂H₅ Ethyl Greenish blue 253 Chloro EthoxyHydrogen (CH₂)₂—O—C₂H₅ Methyl , Greenish blue 254 Bromo Methoxy(CH₂)₂—O-phenyl (CH₂)₂—O-phenyl Methyl Greenish blue 255 Bromo MethoxyC₂H₄ (CH₂)₂—O-phenyl Methyl Greenish blue 256 Bromo Methoxy Hydrogen(CH₂)₂—O-phenyl Ethyl Blue 257 Chloro Methoxy (CH₂)₂—O-benzyl(CH₂)₂—O-benzyl Methyl Greenish blue 258 Chloro Ethoxy (CH₂)₂—O-benzylCH₃ Ethyl Greenish blue 259 Chloro Methoxy (CH₂)₂—O-benzyl HydrogenMethyl Blue 260 Bromo Methoxy (CH₂)₂—O—(CH₂)₃—O—CH₃(CH₂)₂—O—(CH₂)₃—O—CH₃ Methyl Greenish blue 261 Bromo Ethoxy(CH₂)₂—O—(CH₂)₃—O—C₂H₅ (CH₂)₂—O—(CH₂)₃—O—C₂H₅ Methyl Greenish blue 262Bromo Methoxy CH₂—COO—CH₃ CH₂—COO—CH₃ Methyl Blue 263 Bromo MethoxyCH₂-phenyl CH₂—COO—CH₃ Ethyl Greenish blue 264 Bromo Methoxy C₂H₄CH₂—COO—CH₃ Methyl Greenish blue 265 Chloro Methoxy CH₂—COO—C₂H₅CH₂—COO—C₂H₅ Methyl Blue 266 Bromo Methoxy (CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₃Methyl Blue 267 Chloro Ethoxy (CH₂)₂—COO—C₂H₅ (CH₂)₂—COO—C₂H₅ MethylBlue 268 Bromo Methoxy (CH₂)₂—COO—CH₃ C₂H₄ Methyl Greenish blue 269Bromo Methoxy (CH₂)₂—COO—CH₃ CH₂-phenyl Methyl Greenish blue 270 BromoEthoxy CH₃ (CH₂)₂—COO—C₂H₅ Methyl Greenish blue 271 Chloro MethoxyHydrogen (CH₂)₂—COO—CH₃ Methyl Blue 272 Bromo Methoxy (CH₂)₂—COO-phenylHydrogen Ethyl Blue 273 Bromo Methoxy (CH₂)₂—COO-phenyl C₂H₄ MethylGreenish blue 274 Bromo Ethoxy (CH₂)₂—COO-phenyl (CH₂)₂—O—CH₃ MethylGreenish blue 275 Chloro Methoxy (CH₂)₂—COO-phenyl CH₂-phenyl MethylGreenish blue 276 Chloro Methoxy Hydrogen (CH₂)₂—COO-benzyl Methyl Blue278 Chloro Methoxy CH₃ (CH₂)₂—COO-benzyl Ethyl Greenish blue 279 ChloroMethoxy (CH₂)₂—CN (CH₂)₂—COO-benzyl Methyl Blue 280 Bromo Methoxy(CH₂)₂—CN (CH₂)₂—CN Methyl Blue 281 Chloro Methoxy Hydrogen (CH₂)₂—CNEthyl Blue 282 Bromo Methoxy (CH₂)₂—COO—CH₂—CO—CH₃ C₂H₅ Methyl Greenishblue 283 Bromo Methoxy (CH₂)₂—COO—CH₂—CO—CH₃ CH₂-phenyl Methyl Greenishblue 284 Bromo Methoxy Hydrogen (CH₂)₂—COO—CH₂—CO—CH₃ Methyl Blue 285Bromo Methoxy (CH₂)₂—COO—CH₂—CO—C₂H₅ CH₃ Methyl Greenish blue 286 BromoMethoxy (CH₂)₂—COO—CH₂—CO-phenyl C₂H₅ Methyl Greenish blue 287 BromoMethoxy Hydrogen (CH₂)₂—COO—CH₂—CO-phenyl Methyl Blue 288 Bromo Ethoxy(CH₂)₂—COO—CH₂—CO-benzyl C₂H₅ Methyl Greenish blue 289 Chloro MethoxyHydrogen (CH₂)₂—COO—CH₂—CO-benzyl Methyl Blue 290 Bromo Methoxy(CH₂)₂—OCO—CH₃ (CH₂)₂—OCO—CH₃ Methyl Blue 291 Chloro Methoxy(CH₂)₂—OCO—C₂H₅ (CH₂)₂—OCO—C₂H₅ Methyl Blue 292 Bromo Methoxy(CH₂)₂—OCO—CH₃ C₂H₄ Methyl Greenish blue 293 Bromo Methoxy(CH₂)₂—OCO—CH₃ CH₂-phenyl Methyl Greenish blue 294 Bromo Ethoxy Hydrogen(CH₂)₂—OCO—CH₃ Ethyl Blue 295 Bromo Methoxy (CH₂)₂—OCO-phenyl HydrogenMethyl Blue 296 Bromo Methoxy (CH₂)₂—OCO-phenyl C₂H₄ Methyl Greenishblue 297 Chloro Methoxy (CH₂)₂—OCO-phenyl (CH₂)₂—O—CH₃ Methyl Greenishblue 298 Bromo Methoxy (CH₂)₂—O—CH₂—(2-furfuryl) CH₂-phenyl MethylGreenish blue 299 Bromo Methoxy (CH₂)₂—O—CH₂—(2-furfuryl) C₂H₄ MethylGreenish blue 300 Bromo Methoxy (CH₂)₂—O—CH₂—(2-furfuryl)(CH₂)₂—COO—C₂H₅ Methyl Greenish blue 301 Bromo MethoxyCH₂—COO—CH₂—(2-furfuryl) CH₂—COO—C₂H₅ Methyl Blue 302 Bromo Methoxy(CH₂)₂—COO—CH₃ (CH₂)₂—COO—CH₂—(2-furfuryl) Methyl Blue 303 Bromo MethoxyHydrogen CH(CH₃)—CH₂—COO—CH₃ Methyl Blue 304 Chloro MethoxyCH(CH₃)—CH₂—O—CH₃ Hydrogen Methyl Blue 305 Chloro Methoxy HydrogenCH(CH₃)—CH₂—O—C₂H₅ Methyl Blue 306 Chloro MethoxyCH(CH₃)—CH₂—COO—CH₂—CO—CH₃ Hydrogen Methyl Blue 307 Bromo MethoxyCH(CH₃)—CH₂—COO—CH₂—CO—CH₃ CH₂-phenyl Ethyl Greenish blue 308 BromoMethoxy Hydrogen CH(CH₃)—CH₂—COO—CH₂—CO-phenyl Methyl Blue 309 BromoMethoxy CH(CH₃)—CH₂—OCO—CH₃ Hydrogen Methyl Blue 310 Bromo MethoxyCH(CH₃)—CH₂—OCO—C₂H₅ C₂H₄ Methyl Greenish blue 311 Bromo MethoxyHydrogen CH(CH₃)—CH₂—OCO-phenyl Methyl Blue 312 Bromo MethoxyCH(CH₃)—CH₂—COO—CH₂—CO—CH₃ Hydrogen Methyl Blue

1.-17. (canceled)
 18. A dye of formula (I)

wherein X is hydrogen or halogen and K is an aromatic or heteroaromaticcoupling component and wherein the dye:

is excluded.
 19. The dye according to claim 18, wherein X is hydrogen orhalogen, K is selected from the group consisting of aminobenzene,napht-1-yl, napht-2-yl, quinoline or any other N-heterocyclic fused ringsystem, each of which may be unsubstituted or substituted, and a phenol-or naphthol-radical, each of which may be unsubstituted or substituted.20. The dye according to claim 18, wherein X is hydrogen or halogen, Kis a radical of formula (2)

wherein independent from each other R¹ is hydrogen, unsubstituted orsubstituted C₁-C₄-alkyl, unsubstituted or substituted C₁-C₄-alkoxy,chloro, bromo, benzyloxy or O—(CH₂)_(n)-A¹-C₁-C₄-alkyl, R² is hydrogen,hydroxyl, unsubstituted or substituted C₁-C₄-alkyl, unsubstitutedC₁-C₄-alkoxy, chloro, bromo, acyloxy, acylamino or alkylsulfonylamino,wherein n is 1 to 4 and A¹ is O, O—CO, O—CO—O or CO—O and R³ and R⁴ isunsubstituted or substituted C₁-C₄-alkyl, unsubstituted or substitutedphenyl, unsubstituted or substituted benzyl or R¹ and R³ together form a5- or 6-membered aliphatic, heteroaliphatic, aromatic or heteroaromaticring, which 5- or 6-membered ring is unsubstituted or substituted. 21.The dye according to claim 18 having formula (II)

wherein independent of each other X is hydrogen, chloro or bromo, R¹ ishydrogen, hydroxyl, C₁-C₄-alkyl, bromo, chloro or C₁-C₄-alkoxy, R² ishydrogen, hydroxyl, carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen,acyloxy, acylamino or sulfonylamino, R³ and R⁴ is hydrogen, C₁-C₄-alkyl,(CH₂)_(n)-phenyl, CH₂—CH═CH₂, (CH₂)_(n)—OH, (CH₂)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O-phenyl, (CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)—2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p) phenyl, CHR²—CH═CH₂, CHR²—(CH₂)_(p)—OH,CHR²—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COOH,CHR²—(CH₂)_(p)—COO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—COO-phenyl,CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—COO(CH₂)_(p)—(CHR²)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl,CHR²—(CH₂)_(p)—O—CO-benzyl, COO—CHR²—(CH₂)_(p)-2-furfuryl,COO—CHR²—(CH₂)_(p)-2-dehydropyranyl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-dehydropyranyl, whereby all benzyl andphenyl rings can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen,nitro, cyano or COOR² n is 1 to 4, m is 1 to 4 and p is 0 to
 3. 22. Thedye according to claim 21, having formula (II) wherein independent fromeach other X is hydrogen, chloro or bromo, R¹ is hydrogen, methyl ormethoxy, R² is hydrogen, hydroxy, COOH, COO—C₁-C₂-alkyl, C₁-C₂-alkyl,C₁-C₂-alkoxy, chloro, bromo, —NHCO—C₁-C₂-alkyl, —NHCO-aryl,—NHCO-benzyl, —NHSO₂—C₁-C₂-alkyl or —NHSO₂-aryl, R³ and R⁴ is hydrogen,C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)₂—O—(CH₂)_(m)—O-phenyl, (CH₂)₂—O—(CH₂)_(m)—O-benzyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—CH═CH₂,CHR²—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO-phenyl, CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl orCHR²—(CH₂)_(p)—O—CO-benzyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.23. The dye according to claim 21, having formula (II) whereinindependent from each other X is hydrogen, chloro or bromo, R¹ ishydrogen, methyl or methoxy, R² is hydrogen, hydroxy, COOH,COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl, chloro, bromo, NHCO—(C₁-C₂)-alkyl,NHSO₂—(C₁-C₂)-alkyl, R³ and R⁴ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl,CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—O—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—O—CO-phenyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(p)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl, CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkylor CHR²—(CH₂)_(p)—O—CO-phenyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.24. The dye according to claim 18, having formula (III)

wherein independent from each other X is hydrogen, chloro or bromo, R¹is hydrogen, C₁-C₄-alkyl, bromo, chloro or C₁-C₄-alkoxy, R⁵ is hydrogenor C₁-C₄-alkyl, R³ and R⁴ is hydrogen, C₁-C₄-alkyl, (CH₂)_(n)-phenyl,CH₂—CH═CH₂, (CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl,(CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,—(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl CHR²—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)-phenyl, CHR²—CH═CH₂, CHR²—(CH₂)_(p)—OH,CHR²—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR²—(C₂)_(p)—O—(CH₂)_(m)—O-phenyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl,CHR²—(CH₂)_(p)—COOH, CHR²—(CH₂)_(p)—COO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—COO-phenyl, CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—COO(CH₂)_(p)—(CHR²)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(p)—(CHR²)_(m)—O-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl,CHR²—(CH₂)_(p)—O—CO-benzyl, COO—CHR²—(CH₂)_(p)-2-furfuryl,COO—CHR²—(CH₂)_(p)-2-dehydropyranyl,CHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl orCHR²—(CH₂)_(p)—O—(CH₂)_(n)-2-dehydropyranyl, whereby all benzyl andphenyl rings can be substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,halogen, nitro, cyano or COOR², n is 1 to 4, m is 1 to 4 and p is 0 to3.
 25. The dye according to claim 24 of formula (III), whereinindependent from each other X is hydrogen, chloro or bromo, R¹ ishydrogen, methyl or methoxy, R⁵ is methyl or ethyl, R³ and R⁴ ishydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)₂—O—(CH₂)_(m)—O-phenyl, (CH₂)₂—O—(CH₂)_(m)—O-benzyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,COO—(CH₂)_(n)-2-dehydropyranyl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-dehydropyranyl, CHR²—CH═CH₂,CHR²—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O-phenyl,CHR²—(CH₂)_(p)—O-benzyl, CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁₋C₂)-alkyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR²—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO-phenyl, CHR²—(CH₂)_(p)—COO-benzyl, CHR²—(CH₂)_(p)—CN,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR²—(CH₂)_(p)—O—CO-phenyl orCHR²—(CH₂)_(p)—O—CO-benzyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.26. The dye according to claim 24 of formula (III), wherein independentfrom each other X is hydrogen, chloro or bromo, R¹ is hydrogen, methylor methoxy, R⁵ is methyl, R³ and R⁴ is hydrogen, C₁-C₂-alkyl,(CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl,(CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—O—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—O—CO-phenyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR²—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR²—(CH₂)—O—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(p)—CO—(C₁-C₂)-alkyl,CHR²—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl, CHR²—(CH₂)_(p)—O—CO—(C₁-C₂)-alkylor CHR²—(CH₂)_(p)—O—CO-phenyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.27. A process for the production of the dye of formula (I) and mixturesthereof

comprising: a) diazotizing

wherein X is defined as above and b) coupling the diazonium saltobtained in step a) with compounds of formula (2)

wherein R¹ is hydrogen, unsubstituted or substituted C₁-C₄-alkyl,unsubstituted or substituted C₁-C₄-alkoxy, chloro, bromo, benzyloxy orO—(CH₂)_(n)-A¹-C₁-C₄-alkyl, R² is hydrogen, hydroxyl, unsubstituted orsubstituted C₁-C₄-alkyl, unsubstituted C₁-C₄-alkoxy, chloro, bromo,acyloxy, acylamino or alkylsulfonylamino, wherein n is 1 to 4 and A¹ isO, O—CO, O—CO—O or CO—O and R³ and R⁴ is unsubstituted or substitutedC₁-C₄-alkyl, unsubstituted or substituted phenyl, unsubstituted orsubstituted benzyl or R¹ and R³ together form a 5- or 6-memberedaliphatic, heteroaliphatic, aromatic or heteroaromatic ring, which 5- or6-membered ring is unsubstituted or substituted.
 28. A chemicalcomposition comprising one or more dye(s) according to claim
 18. 29. Achemical composition consisting of two or more dyes according to claim18.
 30. An aqueous dispersion for dying comprising one or more dyesaccording to claim
 18. 31. A process for dyeing or printing hydrophobicmaterials with the dye according to claim
 18. 32. An ink for digitaltextile printing comprising the dye according to claim
 18. 33. Use ofthe dye according to claim 18 for dying fibers which comprisescontacting the fibers with the dye according to claim 18, wherein thefibres are selected from the group consisting of: synthetic fibermaterials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetablefibres, seed fibres, cotton, organic cotton, kapok, coir from coconuthusk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres,sisal, henequen, banana; stalk fibres, bamboo; fibres from animals,wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angorafibre as well as fur and leather materials; manufactured, regeneratedand recycled fibres, cellulosic fibres; paper fibres, cellulosicregenerated fibres, viscose rayon fibres, acetate and triacetate fibersand Lyocell fibers.
 34. Fiber and blends comprising a fiber selectedfrom the group consisting of: synthetic fiber materials, nylonmaterials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seedfibres, cotton, organic cotton, kapok, coir from coconut husk; bastfibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal,henequen, banana; stalk fibres, bamboo; fibres from animals, wool,organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre aswell as fur and leather materials; manufactured, regenerated andrecycled fibres, cellulosic fibres; paper fibres, cellulosic regeneratedfibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocellfibers and comprising one or more dye(s) according to claim 18 either inchemically and/or physically bound form.